Modification of polymer optoelectronic properties after film formation by impurity addition or removal

ABSTRACT

The methods of this invention involve modification of the properties of an organic film after it has been deposited by either adding new components into it from its top or bottom surface, or by causing components to leave the film from its top or bottom surface. In the examples of these methods, the emitting color of light-emitting diodes are modified based on doped polymers by locally introducing dopants causing different color emission into the film by local application of a solution containing the desired dopant to the film surface (by ink jet printing, screen printing, local droplet application, etc.). This overcomes difficulties encountered with the direct patterning of three separately formed organic layers (each which uniformly coats an entire surface when formed) into regions for separate R, G, and B devices due to the sensitivities of the organic materials to chemicals typically used with conventional patterning technologies. Alternatively, dopants may be introduced in an organic film by diffusion from one layer into the film. Alternatively, dopants may be selectively removed from a film with solvents, etc.

This application is a national application under 35 U.S.C. § 371 basedupon PCT/US99/07970, which was filed on Apr. 12, 1999, and claimspriority to provisional application 60/081,492, filed on Apr. 13, 1998.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to methods of making semiconductor devicesusing light emitting organic materials, and more specifically, tomethods which involve the modification of the properties of an organicfilm after it has been deposited by either: (i) adding new componentsinto the film from a top or bottom surface; or (ii) by causingcomponents to leave the film from a top or bottom surface.

2. Related Art

Polymers and blends of polymers and small organic molecules haverecently been extensively used to fabricate organic light emittingdiodes and thin film transistors.

Organic films are typically deposited in thin film form for electricaland optoelectronic applications by uniformly coating a surface byspin-coating or other methods. Sometimes the final organic film itselfis not directly formed, but a precursor is deposited which is convertedto a polymer by a subsequent step, such as heating or exposure to UVlight (e.g. PPV). It is also well known that adding various elements tothe organic film can change its electrical and/or optical properties.These may include elements to change the conduction of electricalcarriers (e.g. PBD for electron transportability), or dye centers tochange the color of photo- and electro-luminescence (e.g. coumarin 6 inPVK). These extra elements are usually added to the original materialbefore the final solid film is deposited. For example, these differentgroups could be bonded to a polymer chain before the polymer isdeposited by spin coating, or may just be added as other polymers orindividual smaller molecules to the solution containing the polymerbefore a thin film is formed. In either case all materials in theoriginal solution become part of the final film.

The goal of fabricating full color flat panel displays has the potentialto be reached using organic light emitting diodes (OLEDs). Thedifficulty with using this technology is that the current depositiontechniques, such as spin-coating and evaporation, deposit blanket films.The film can be used to make devices of a single color. To achieveindividual emitters of different color next to each other, such as red,green, and blue, the deposited blanket film must be typically etchedinto a pattern, as might be done by photolithography followed byetching. Then, this process has to be repeated for multiple layers toachieve full color (red, green and blue emitters). Etching of organicfilms and photoresist processing for lithography on organic films hasproven to be technically very difficult and expensive. Therefore,instead of making a blanket film of one color, etching and making ablanket film of another color, it would be beneficial to make oneblanket film and later locally change the properties of the film to emitdifferent light colors. Thus, the need for etching would be removed.

Another approach is ink-jet printing local regions, but a problemassociated with ink-jetting printing is that the dots printed do nothave a uniform thickness.

Accordingly, what is desired, and has not heretofore been developed, isa method to modify the properties of a film after it has been formed, byintroducing therein or removing impurities to modify the propertiestherefrom.

OBJECTS AND SUMMARY OF THE INVENTION

An object of the present invention is to provide a method formanufacturing optoelectronic organic films having locally modifiedareas.

Another object of the present invention is to provide an organic filmwith various regions of modified optoelectronic properties.

Still another object and advantage of the invention is to form anorganic film with modified properties by applying dopants in desiredplaces.

A further object and advantage of the invention is the provision of amethod for forming an organic film with local modified areas by addingimpurities to or removing impurities from the film.

Even another object of the invention is to provide a method for locallymodifying properties of an organic film without the need forphotolithography and etching of the organic film.

A still further object and advantage of the invention is the provisionof a method for manufacturing a locally modified organic film with theneed for contacting the surface of said film with solvents.

Even an additional object of the invention is to provide a process offorming a locally modified organic film wherein dopant is added to thefilm in an annealing process.

Yet an additional object of the present invention is to provide aprocess for transferring a dopant from one layer to another layer.

A further object of this invention is the provision of a process fortransferring a dopant from one layer to another layer in a desiredpattern.

The methods of this invention involve modification of the properties ofan organic film after it has been deposited by either adding newcomponents into it from its top or bottom surface, or by causingcomponents to leave the film from its top or bottom surface. In theexamples of these methods, the emitting color of light-emitting diodesare modified based on doped polymers by locally introducing dopantscausing different color emission into the film by local application of asolution containing the desired dopant to the film surface (by ink jetprinting, screen printing, local droplet application, etc.). Thisovercomes difficulties encountered with the direct patterning of threeseparately formed organic layers (each which uniformly coats an entiresurface when formed) into regions for separate R, G, and B devices dueto the sensitivities of the organic materials to chemicals typicallyused with conventional patterning technologies. Alternatively, dopantsmay be introduced in an organic film by diffusion from one layer intothe film in local regions or by locally applying them directly into theorganic film. Alternatively, dopants may be selectively removed from afilm with solvents, etc.

Typically all of the active components are incorporated into the polymerwhen the polymer film is first formed, for example by spin coating itover a surface. In the present invention, the properties of the materialare modified after a solid film has been formed by later introducing newspecies into the film from either its top or bottom surface, or removingimpurities out through the top or bottom surface especially in apatterned arrangement. The method is especially attractive for the localmodification of the photoluminescence and/or electroluminesence color ofa thin film of the material, for example to create red, green, and bluelight-emitting regions after a surface has been coated with a thin filmof the material which is the same everywhere.

BRIEF DESCRIPTION OF THE DRAWINGS

Other important objects and features of the invention will be apparentfrom the following Detailed Description of the Invention taken inconnection with the accompanying drawings in which:

FIGS. 1 a and 1 b are diagrams of the application of dye on top of PVKfilm.

FIGS. 2 a and 2 b are diagrams of dye on PVK film under UV illumination.

FIG. 3 is a plot of photoluminescence of materials used in FIGS. 1–2.

FIG. 4 a is a diagram of a device and FIG. 4 b is a plot of theelectroluminsence spectra of PVK and C6.

FIGS. 5 a and 5 b are diagrams of removal of local dye with acetone.

FIG. 6 a is a diagram of a device and FIGS. 6 b and 6 c photographs ofthe device of FIG. 6 a under UV illumination.

FIG. 7 is a photograph under UV illumination of a device fabricated withan ink jet printer;

FIG. 8 a is an experiment showing the effects of temperature on devicesfabricated in accordance with the invention, and FIG. 8 b is plotthereof.

FIG. 9 is a photograph under UV illumination of a device formed inaccordance with the invention at increasing temperatures.

FIGS. 10 a–10 c illustrate the steps in introducing film dopants fromthe top.

FIGS. 11 a–11 c illustrate the steps in introducing dopants from thebottom.

FIGS. 12 a–12 c illustrates the steps for spatially modifying propertiesof polymer film.

FIGS. 13 a–13 b illustrate the spectra of PVK and PVK with C6.

FIGS. 14 a–14 c illustrate the steps in removing dopant from a polymerfilm into the underlying layer.

FIGS. 15 a–15 c illustrate the steps in forming patterned addition ofdopant from the top.

FIGS. 16 a–16 c illustrate the steps in fabrication of patterned OLEDs.

FIGS. 17 a–17 d illustrate the steps in fabrication of a passive matrix.

FIGS. 18 a–18 c illustrate the steps in removal of dopant from polymerfilm in a pattern to the underlying layer.

FIGS. 19 a–19 b illustrate the steps in removal of dopant from the topof a film.

FIGS. 20 a–20 c illustrate the steps in the patterned removal of dopantfrom the top of a film.

FIGS. 21 a–21 d illustrate the steps in fabrication of an active matrixOLED display.

DETAILED DESCRIPTION OF THE INVENTION

The goal of fabricating full color flat panel displays has the potentialto be reached using organic light emitting diodes (OLEDs). Thedifficulty with using this technology is that the current depositiontechniques, such as spin-coating and evaporation, deposit blanket films.The film can be used to make devices of a single color. To achieveindividual emitters of different color next to each other, such as red,green, and blue, the deposited blanket film must be typically etchedinto a pattern, as might be done by photolithography followed byetching. Then, this process has to be repeated for multiple layers toachieve full color (red, green and blue emitters). Etching of organicfilms and photoresist processing for lithography on organic films hasproven to be technically very difficult and expensive. Therefore,instead of making a blanket film of one color, etching and making ablanket film of another color, it would be beneficial to make oneblanket film and later locally change the properties of the film to emitdifferent light colors. Thus, the need for etching would be removed.

The present invention, in a broad, general sense, relates to theapplication of an organic film and thereafter modifying localcharacteristics thereof by adding or removing components, i.e. dopants,dyes, etc., to or from the film to change the local characteristics ofthe film. Specifically, the invention relates to modifying theoptoelectronic properties of an organic film by impurity or additionalremoval in a patterned fashion after application of the film. Even morespecifically, the invention relates to modifying the emitting color oflight-emitting diodes based on doped polymers by locally introducingdopants causing different color emission into an organic film by localapplication of solutions containing desired dopants to the film surface,i.e. by ink-jetting or screen printing. Alternatively, impuritiescontained within the film prior to application can be removed therefromin desired patterns through various methods such as by application ofsolvents.

One way for achieving this result is to locally dye apoly(9-vinylcabazole) (PVK a hole transporting polymer) spun-on film,with green, red and blue dyes. The dyes would dissolve in acetone ortrichloroethylene (TCE), solvents that do not dissolve PVK, and could bepatterned on top of the PVK film using an ink-jet printer. As shown inFIGS. 1 a and 1 b, the dopants diffuse into the film and the solventevaporates. Then metal cathodes could be patterned on top of the locallydyed regions, thus achieving full color integration.

To verify this technique, droplets of coumarin 6 (C6, a green dye)dissolved in TCE and Acetone were placed onto a spun-on 1000 angstromthick PVK film using a pipette and the solvents were given time toevaporate. FIG. 2 a shows a picture of these drops taken from above witha UV lamp shining on them to excite fluorescence of the organic film.Under UV, they appear to be a greenish yellow color. These droplets werealso placed onto glass where no diffusion occurs and the C6 remains onthe surface, and the solvents were allowed to evaporate, as shown inFIG. 2 b. Under UV lamp they appear to be a reddish color. Thisindicates that when the drops are placed onto a PVK film there is someinteraction with the PVK, because when the PVK is present the dyed areasappear greenish-yellow, and when the PVK is not present the dye appearsred. The interaction is the diffusion of the dye into PVK.

In order to state the above observations in a more quantitative way, aphotoluminescence spectra was taken. FIG. 3 shows the PL spectra of apure PVK film (peak at 410 nm), a PVK film locally dyed with C6 (peak at490 nm), a blend film, where the PVK was dyed in solution with C6 (peaka 490 nm), and the dye on glass (peak at 580 nm). This provides evidencethat not only does the dye interact with the PVK, but it interacts insuch a way that the PL spectra is nearly identical to that of a blendfilm, which is known to be able to be made into a device. Therefore, thenext step was to attempt to make a device using this locally dyeingprocedure.

FIG. 4 a shows the device structure, and FIG. 4 b shows theelectro-luminescence (EL) spectrum of the device and the EL of a blenddevice made by dissolving PVK and C6 in chloroform, spinning the film,and evaporating contacts. To make the locally dyed device, PVK dissolvedin chloroform was spun onto glass coated with indium tin oxide (ITO, atransparent conductor). Next, a drop of C6 dissolved in acetone wasdropped onto the surface, the sample was then spun again. Finally, ametal contact was evaporated on top of the dyed area. The EL spectra ofthe locally dyed device is seen to have the same 490 nm peak as theblend device Therefore, this shows that the dye not only interacts withthe PVK, but it interacts in such a way that a device can be made whichhas a similar EL spectra to blend device.

In order to further investigate this locally dyeing phenomenon, anexperiment was set up to see if dye could be washed out of a blend film,which had been dyed in solution. FIGS. 5 a and 5 b shows a schematic ofthe experiment. First, PVK and C6 were dissolved in chloroform. Next,they were spun-on to an ITO coated glass substrate, forming a 1000angstrom film. When this film was observed under a UV lamp, it appearedgreen. Next, a drop of acetone was dropped onto the surface. When a UVlamp was shone onto the sample, it was observed that where the drop ofacetone had been, the sample was blue, and where it had not been, thesample was green. This indicates that the dye could be washed out of ablend film, which created a local area without dye. Therefore, twodifferent color LEDs could be made on a substrate which had been locallywashed.

FIG. 6 a shows a schematic of the device made on the washed film. Thefilm was prepared as mentioned above, and then metal cathodes wereevaporated in the washed areas and in the non-washed areas. Thesecathodes were thermally evaporated and were patterned by a shadow mask.FIGS. 6 b and 6 c are pictures of the devices, from below, emittinglight. FIG. 6 b shows a device emitting green (appears light bluebecause of camera used) and FIG. 6 c shows an emitting blue. The greendevice is emitting green because the metal cathode was evaporated on topof the dyed film, and the blue device is emitting blue, because themetal cathode was evaporated on top of the washed film.

Thus, devices can be made by locally dyeing a PVK film, or by locallywashing a dyed PVK film. Therefore, the next step is to pattern the dyeusing an ink-jet printer. FIG. 7 shows a picture of a piece of glasscoated with ITO, onto this glass was spun a 1000 angstrom thick film ofPVK. Then an Epson Stylus Color 400 ink-jet printer was used to patternC6 dissolved in acetone on top of the film. The sample was thenilluminated under UV. This shows that the dyes can be patterned by anink-jet printer with a spot diameter of ˜500 μm. The next step is to tryto determine the ultimate resolution of this technique.

An experiment was done to determine if the diameter of the printed spotscould be influenced by temperature. FIG. 8 a shows the experimentalset-up, a 1000 angstrom film of PVK was spun onto a piece of glasscoated with ITO. The sample was then placed onto a hot plate. Dropletsof equal volume of C6 dissolved in acetone and equal volumes of C6dissolved in TCE were dropped on to the PVK film at differenttemperatures. It was observed that at higher temperatures the spots didnot spread as far and therefore had smaller diameters. This is shown inthe plot of FIG. 8 b. This could potentially make the spot size ˜0.6times smaller. However, this data does not reveal the differenceobserved in using TCE and acetone.

FIG. 9 shows a picture of the same spots dropped onto the PVK film atincreasing temperatures lit up by a UV lamp. What can be seen is thatthere are, at higher temperatures in the TCE drops, bright yellow spotswhich are ˜⅓ of the outer spot, and have a more intense luminescence.This may be because, as the solvent dries the C6 tends to stay in thesolution and what is left at the end is a highly concentrated smalldiameter spot. When this spot profile is checked using a surfaceprofilometer it is seen that the dye is actually sitting on the surface.Therefore, in order to take advantage of this small diameter, thesubstrate would have to be heated further, to allow the dye to thermallydiffuse into the film.

In conclusion, PVK can be locally dyed by dissolving dye in acetone orTCE and dropping it on to the surface. Also, this dyed area can be madeinto a device. A blend film of PVK and C6 can have the C6 locally washedout of it using acetone, and a device can be made using this technique.At the present time ink-jet printed dyed lines can be made with widthsof ˜500 μm. This width can be further reduced by printing with TCE ontoa heated substrate to obtain a spot 1/10 of the diameter of a spot madeat room temperature. This substrate would have to then be heated againto thermally diffuse the dye into the film.

FIGS. 10 a–10 c illustrate the basic method for introducing film dopantsfrom the top in the fabrication of red, green and blue OLED devices on acommon substrate. As shown in FIG. 10 a, a uniform film of polymer 10without the desired dopant is formed on substrate 11. The polymer film10 may contain other dopants. In FIG. 10 b, dopant 12 is placed on thesurface of the polymer film 10 by evaporation, spin coating, or othermethod. In FIG. 10 c annealing or other process caused the dopant 12 toenter the film 10 by diffusion or by other methods. The solvents used inspin coating the dopant 12 on the surface may cause dopant 12 to enterpolymer 10 and be deposited into it without need for the steps describedin FIG. 10 c. In this case there is never a solid dopant layer on thesurface.

FIGS. 11 a–11 c show the introduction of dopants into a film from thebottom thereof. In FIG. 11 a, a substrate 13 has a coating 14 put downthereon. The coating 14 may contain the desired dopant or, the dopantmay be applied in the manner described in FIGS. 10 a–10 c (i.e. may bepolyanaline or similar hole transport layer in OLED). As shown in FIG.11 b, the polymer film 15 is deposited onto the coating 14. In FIG. 11c, annealing causes dopant to partially migrate from layer 14 intopolymer film 15. It should be noted that the solvents used in spincoating the top polymer may “leach” dopant out of the underlying layerwithout the need for the thermal cycling described in FIG. 11 c.

FIGS. 12 a–12 c show the steps of a method for spatially modifying theproperties of the polymer film. FIG. 12 a illustrates the deposition ofa polymer 16 onto a substrate 17 in the same manner as discussed inconnection with FIG. 10 a. FIG. 12 b shows the creation of local regionsof different dopants, 18 and 19 on the polymer surface 16 by localdeposition methods such as evaporation through different shadow masks,deposition by screen printing using different screens, or by ink jetprinting, or other printing processes using different patterns for eachdopant. FIG. 12 c illustrates the heat treatment of the structures ofFIG. 12 b by annealing, for example, to cause the dopant 18 and 19 tomigrate into the polymer 16. As discussed in connection with FIGS. 10a–10 c, solvents used in screen printing or in ink jet printing maycarry dopants directly into the polymer so that the heat treatment stepof FIG. 12 c may not be required.

This has been demonstrated using dyes C6 (green), C47 (blue), and nilered (green) in acetone solution separately applied to individual regionsof a single PVK film, where acetone solution is locally applied by aneyedropper or similar device. Acetone does not cause removal of PVKfilm, but after evaporation of acetone in a few seconds the fluorescencecolor of the film under UV excitation has changed.

As illustrated in FIGS. 13 a–13 b, both the photoluminescence (FIG. 13a) and electroluminesence (FIG. 13 b) show the shift between pure PVKfilm and doped PVK.

The dopant need not be pure dopant, but may be co-deposited with anothermaterial. Subsequent process (or the very deposition process itself) canthen cause dopant to move into underlying layer. Other material may beremoved or remove itself (evaporate), or stay behind as separate layerand be part of final structure doped or undoped.

The spatial variations of FIGS. 12 a–12 c, may be applied to the methoddescribed in connection with FIGS. 11 a–1 c so that patterns of dopantmay be introduced into underlying material before top polymer film isdeposited.

FIGS. 14 a–14 c illustrate the steps in the removal of dopant frompolymer film into an underlying layer. In FIG. 14 a, substrate 19 has abottom absorber film layer 20 deposited thereon. The absorber layer hasa low chemical potential for the desired dopant. In FIG. 14 b, the dopedpolymer 21 is deposited onto the absorber layer 20. In FIG. 14 c,annealing or another cycle which causes the dopant to move is applied.In lieu of the heating treating, a solvent may be applied whichinfiltrates (from the top) both the polymer layer 21 and the bottomlayer 20 to enable the dopant in the top polymer layer to migrate intothe bottom layer 20.

FIGS. 15 a–15 c shown the patterned addition of dopant from the top withan impermeable barrier. In FIG. 15 a, the undoped polymer 23 isdeposited on substrate 22. In FIG. 15 b, a patterned layer impermeableby the dopant 24, 25, 26 is formed on the top of the polymer 23. In FIG.15 c dopant 27 in ambient is heat treated by annealing. Alternatively,the structure of FIG. 15 b may be placed into a solvent containing thedopant

FIGS. 16 a–16 c illustrate the application of the method described inFIG. 12 to the formation of patterned OLEDs of different colors. Asshown in FIG. 16 a, undoped polymer 30 is deposited everywhere onto ITOlayer 29 on glass substrate 28. The ITO may be patterned. Local red(31), green (32) and blue (33) regions are formed by locally doping thepolymer 30. These red, green and blue regions may be formed by ink jetprinting three different solutions in different regions. Heat treatingmay then be applied. In FIG. 16 c, top contacts 34, 35, 36 are formed onthe red, green, and blue regions by standard methods such as byevaporation through a shadow mask. In making OLED's applying colordopant by using localized solvent may change any dopants which were infilm from original spin coating (e.g. PBD for electron transport). So,some of this dopant may need to be put in with the color dopantsolution.

FIGS. 17 a–17 d illustrate the application of the method described inFIG. 12 to form a passive matrix color OLED display. In FIG. 17 a, ITOlines 37 are formed in one direction on glass substrate 38. In FIG. 17b, a uniform polymer film 39 is applied over the ITO lines. In FIG. 17c, red, green, blue doped polymer 40 is formed on the ITO lines in thepolymer film as by the steps described in FIG. 16 b. FIG. 17 d cathodelines 41 as top contacts perpendicular to the bottom contact lines 37.Doping need only be in the region of the intersection of the top andbottom contact lines.

FIGS. 18 a–18 c illustrate the removal of dopant from polymer film in apattern to the underlying layer. In FIG. 18 a, the absorber film 43 isdeposited onto substrate 42. In FIG. 18 b, absorber film 43 is patternedor coated with a patterned impervious layer 44. Doped polymer 45 isadded onto the layer 44. FIG. 18 c shows the effect of annealing orother treatment of the structure of FIG. 18 b in causing the doping tomove into the underlying layer 43, where it is not impeded by theimpervious barrier. The movement of the dopant may be accomplishedthrough the use of a solvent as discussed in connection with FIG. 14 c.

FIGS. 19 a–19 b shows the removal of dopant from the top of anunpatterned film. In FIG. 19 a, doped film 47 is deposited onto asubstrate 46 as by spin coating with dopant in solution. FIG. 19 billustrates the treatment of the structure of FIG. 19 a by annealing incertain ambients or washing with solvent to the cause the reduction ofdopant in layer 47. Washing by applying the drop may not remove thedopant from the film, but cause it to move to the edge of the droplocation, leaving little dopant in the center of the drop.

FIGS. 20 a–20 c illustrate the patterned removal of dopant from the topof the film. In FIG. 20 a, doped polymer film 49 is deposited ontosubstrate 48. In FIG. 20 b patterned impermeable layer 50 is appliedover the doped polymer layer 49. In FIG. 20 c, annealing the structureof FIG. 20 b causes dopant to evaporate in areas without barrier 50.This evaporation may also be accomplished by washing with solvent toremove dopant in the areas without barrier 50, or treating with asolvent vapor.

FIGS. 21 a–21 d show the formation of an active matrix OLED display. InFIG. 21 a, glass substrate 51 has patterned insulator 52 and electrodes53 formed thereon. The electrodes are connect to transistors (not shown)in the pixels. In FIG. 21 b, undoped organic layer 54 is depositedeverywhere on the structure of FIG. 21 a. In FIG. 21 c, locally appliedred (55), green (56) and blue (57) dopant is applied as by ink jetprinting. As shown in FIG. 21 d, top electrode 58 is applied without apattern. Top electrode 58 may be, for example Al:Li or Mg:Ag cathode.

The methods described in this invention may be applied to any organicfilm, not just polymer based. Solvent methods may cause problems withsmall organic molecule based films, however, dopants could be depositedby diffusion by thermal treatment by other localized methods such asevaporation through a mask, etc.

It should be further understood that “undoped” means not doped with thedopant being added or removed. Other dopants may be present.

Having thus described the invention in detail, it is to be understoodthat the foregoing description is not intended to limit the spirit andscope thereof. What is desired to be protected by Letters Patent is setforth in the appended claims.

1. A method of manufacturing an organic device comprising: providing asubstrate, providing a first electrode disposed on the substrate;applying an organic coating having a dopant over the first electrode;removing the dopant from areas of the coating, wherein the areas of thecoating from which the dopant is removed remain over the first electrodeafter the dopant is removed; and depositing a second electrode over theorganic coating, wherein the dopant is removed from the coating byannealing which causes the dopant to migrate from the coating.
 2. Themethod of claim 1 wherein a mask is patterned on the coating prior toannealing to remove the dopant in a pattern.
 3. A method ofmanufacturing an organic device comprising: providing a substrate,providing a first electrode disposed on the substrate; applying anorganic coating having a dopant over the first electrode; removing thedopant from areas of the coating, wherein the areas of the coating fromwhich the dopant is removed remain over the first electrode after thedopant is removed; and depositing a second electrode over the organiccoating, wherein the dopant is removed from the coating by a solventapplied to the surface of the coating, and wherein a mask is patternedon the coating prior to applying the solvent to remove the dopant in apattern.
 4. A method of manufacturing an organic device comprising:providing a substrate, providing a first electrode disposed on thesubstrate; applying an organic coating having a dopant over the firstelectrode; removing the dopant from areas of the coating, wherein theareas of the coating from which the dopant is removed remain over thefirst electrode after the dopant is removed; and depositing a secondelectrode over the organic coating, wherein the dopant is removed fromthe coating by a solvent applied to the surface of the coating, andwherein the solvent is applied in a pattern onto the coating to removethe dopant in a pattern that does not include the entire area of thecoating.
 5. A method of manufacturing, comprising: providing asubstrate; providing a first electrode disposed over the substrate;providing a first layer having a dopant disposed over the firstelectrode; providing a second layer on the first layer, wherein thesecond layer is organic; transferring the dopant from the first layer tothe second layer; and depositing a second electrode over the secondlayer.
 6. The method of claim 5 wherein the dopant is transferred in apattern from the first layer to the second layer, wherein the patterndoes not include the entire area of the second layer.
 7. The method ofclaim 6 wherein masking means is provided on the first layer prior toproviding the second layer, and the dopant is transferred from the firstlayer to the second layer in areas not masked.
 8. The method of claim 6wherein the first layer with the dopant is patterned, and the dopant istransferred to the second layer in the pattern of the first layer.
 9. Amethod of manufacturing a device comprising: providing a substrate;providing a first electrode disposed over the substrate; providing afirst layer of material; applying a dopant in a pattern to the firstlayer such that the first layer contains the dopant; providing a secondlayer comprising an organic material disposed over the first electrode;transferring the dopant from the first layer to the second layer in thepattern such that the second layer contains the dopant; and providing asecond electrode disposed over the second layer.
 10. The method of claim9 wherein the dopant is applied by application of liquid droplets. 11.The method of claim 10 wherein the liquid droplets are applied byink-jet printing.
 12. The method of claim 9 wherein the dopant isapplied by screen printing.
 13. The method of claim 9 wherein the dopantmodifies the light emitting properties of the organic film.
 14. Themethod of claim 13 wherein the dopant comprises red, green or blue dyes.15. The method of claim 14 wherein the dopant includes coumarin and nilered.
 16. The method of claim 9 wherein the dopant is transferred byannealing.